Ultralong Room-Temperature Phosphorescence from Supramolecular Behavior via Intermolecular Electronic Coupling in Pure Organic Crystals.

Ultralong room-temperature phosphorescence (RTP) of organic materials is extremely attractive for its tremendous potential use. However, the design of organic materials with ultralong and efficient RTP is very challenging due to the lack of general design principles. A new design principle for organic materials with ultralong room-temperature phosphorescence based on π-π-dominated supramolecular aggregates in crystal is proposed, and strong intermolecular electronic coupling with specific molecular alignment is identified to be responsible for supramolecular behavior in persistent emission. Small substituents in molecular structure favor the formation of supramolecular aggregates in the crystal, thus facilitating the generation of ultralong RTP under ambient conditions. Our results also reveal that the introduction of heavy atoms into supramolecular aggregates as a general rule can be used to achieve efficient persistent phosphorescence.